Organometallic Complexes as Models for the Adsorption of Thiophenes on Hydrodesulfurization (HDS) Catalysts

Abstract

In this review are discussed the known modes of thiophene coordination (q'(S), 7 , T and 7f' ) in organometallic complexes. Their structures, bonding and stabilities are related to the adsorption of thiophene on heterogeneous hydrodesulfurkation (HDS) catalysts. Modes of benzo[b]thlophene and dibenzothiophene coordination in organometallic complexes are briefly summarized.2 4

Carbon−Phosphorus Bond Activation of Tri(2-thienyl)phosphine at Dirhenium and Dimanganese Centers

“…A variety of organometallic systems, including transition-metal clusters, have been studied as models for the catalytic HDS of thiophenes since mechanistic information can be easily obtained by spectroscopic and analytical studies of discrete molecular complexes. − As a consequence, a thorough investigation of the reactivity of thiophenes toward transition metal centers has been studied by several groups as models of thiophene adsorption on HDS catalysts. These have been the subject of reviews, although the interaction of thiophenes with the catalyst surface during HDS is not yet properly understood. ,,− On the basis of these studies, it has been proposed that substrate binding to active metal sites through the sulfur atom is an initial step followed by carbon−sulfur bond cleavage. , …”

First-principle investigation of thiophene adsorption on TM (Ni/Co/Mn)-doped (ZnO)15 nanotube

“…The most stable structures after geometry optimizations are obtained. Then, based on the previous studies of IR spectra [29,30], we attempt to consider the g 1 , g 2 and g 5 bonding modes, which are the most commonly cited bonding modes, as the initial structures of thiophene adsorption on TM-doped (ZnO) 15 nanotube on the top of TM atom. The g 1 , g 2 and g 5 bonding modes represent S-bonding to a metal site, p-binding of two carbons and p-binding of all five atoms in the thiophene ring to a metal atom, respectively [31].…”

Heterogeneous Photocatalytic Reactions of Sulfur Aromatic Compounds

“…However, experimental determination of the physicochemical properties of the adsorption complex of sulfur aromatic compounds with the solid sorbent [118] or catalyst [119] is usually quite difficult. [32] Scheme 5 shows the known geometries of thiophene in organometallic compounds; [120] such compounds serve as the "model materials systems" for mechanistic studies of adsorption and catalysis.…”